Method of making random dyed yarns



Feb. 4, 1964 L. E. WEIR 3,

METHOD-OF MAKING RANDOM DYED YARNS Filed Aug. 3, 1961 United States Patent 3,12%,422 METHQD OF MAKING RANDQM DYED YS Lewis E. Weir, Fairmount, Ga, assignor, by mesne assignments, to Astro Dye Works, Inc., Calhoun, Ga., a corporation of Georgia Filed Aug. 3, 1961, Ser. No. 129,026 3 Claims. (Cl. 8-14) The present invention relates to random dyed yarns, and more particularly to improved random dyed cellulosic yarns and to the method of making same.

The yarns of the present invention are particularly characterized in that they are dyed in a true random manner and are fast to washing, peroxide bleaching, light and crocking.

The term true random dyed yarn as used herein is defined as a yarn that is dyed at various places along the yarn, with varying spaces of dyed area, in a nonrepeating pattern, and in fact without any set pattern. Fabrics produced from true random dyed yarns have a random effect, or varying sized dyed areas occurring at irregular intervals, and do not have repeating patterns, recurring patterns, chevron-shaped patterns, stripes, or indeed any set pattern.

The process of the present invention is particularly characterized in that a dye composition comprising essentially fiber reactive dyestuif, alkali and solvent, such as Water, is injected into a wound package of cellulosic yarn and the yarn package is allowed to stand until chemical reaction between the dyestutf and the fibers of the yarn has occurred. One or more injections of the foregoing dyestutt' composition may be made into the yarn package, using various colors as desired.

The dyestuff may be injected into the yarn package by any suitable means, such as a hollow injection needle, forced air, or a perforated cone under pressure.

Dyestuffs heretofore used for random dyeing were not fast to Washing, bleaching or crocking. The lack of wash and crock fastness resulted because the dyestuffs utilized did not become fixed to the fibers of the yarn, and were only insecurely adhered to the surface of the fibers. Fixation could not be carried out in the wound package by the conventional methods of oxidation and steaming. When fabrics that were produced from these non-fast random dyed yarns were washed, the dyestuif bled out into the wash water, causing fading and coloration of the entire fabric.

To overcome the above problem of lack of fastness, the industry resorted to space dyeing. One method of space dyeing comprises winding the yarn into skeins, hanging the skeins on a machine, immersing the various skeins at varying depths into the liquid dyestufr" for a period of time, extracting the liquid dyestuff from the yarn, rehanging the skeins on the machine, again immersing the various skeins at varying depths into a second color, extracting the dyestufl from the yarn, and repeating the rehanging, immersing and extraction for each dyed space desired, and finally drying the yarn and rewinding the yarn into a package. The above described method of space dyeing is undesirable because of the high cost of labor involved, the length of time required, the large amount of equipment which must be utilized, and the loss of dyestuff through incomplete exhaustion of the dyestufr" from the solvent onto the yarn. However, the most serious disadvantage of the above described method of space dyeing yarns is that the fabrics produced from the resulting space dyed yarns have objectionable 3,120,422 Patented Feb. 4, 1964 striped, or repeating and chevron-shaped patterns, because the skein loops have been suspended into the dyestuff.

The most widely used process for producing space dyed yarn is a roller printing process whereby the dyestuff is printed onto the yarn in various colors at varying locations along the yarn, but in a repeating pattern. The principal disadvantage of this process is that an objectionable recurring pattern results in the yarn and in all fabrics produced therefrom, because of the repeating nature of printing rollers. This process is also objectionable because of the high cost involved in engraving or embossing the printing rollers. Each pattern change requires differently engraved or embossed printing rollers, so that it is not commercially practical to produce small quantities of any one yarn by the printing process.

The yarn and method of the present invention are described in detail below in connection with the accompanying drawings in which:

FIG. 1 is a top plan view of a cone of yarn dyed according to the present invention;

FIG. 2 is a front elevational view of the cone of yarn of FIG. 1;

FIG. 3 is a vertical sectional view taken along the line 33 of FIG. 1; and

FIG. 4 is a plan view of a strand of yarn dyed according to the present invention.

The method of the present invention produces yarn that overcomes the above described disadvantages and limitations of the prior art in the following manner.

The yarn 15 of the present invention has dyed areas 12-14 and undyed areas 16, and is fast to Washing, light, crocking and peroxide bleaching. The dyed and undyed areas are of varying lengths and occur at true random. The fiber reactive dyestufi composition penetrates the cellulosic fibers and becomes fixed thereto and therein by chemical reaction. Thus the yarn may be Washed without bleeding and coloration of the undyed areas. Fabrics produced from the yarn of the present invention, such as by tuiting, knitting and weaving, do not have the objectionable, repeating, striped or chevron-shaped patterns that are characteristic of fabrics produced from the above space dyed yarns, because the yarn is dyed in a true random manner, e.g. the dyestulf has become fixed along the yarn in varying lengths of dyed area, with varying lengths of undyed areas between the dyed area. The method utilized in dyeing the yarn is inexpensive because such things as expensive printing and dyeing machinery, extensive labor in hanging and rehanging skeins of yarns, and expensive engraving and embossing of printing rollers is eliminated, and only an inexpensive means of injection, such as a syringe and needle, is required. Also, substantially all of the dyestuif utilized in the present method if exhausted onto the fibers, except for small amounts that are unreacted, resulting in a saving of dyes.

According to the process of the present invention, a dye composition comprising essentially fiber reactive dye, solvent and alkali is injected into a wound package of cellulosic yarn. A wetting agent and a mildew resist agent may be added to the dyestuff composition, and when cotton yarn is to be dyed a wetting agent is especially beneficial to insure maximum penetration of the dyestuif into the yarn. The injected package of yarn is allowed to stand at room temperature until the dyestuif has reacted chemically with the fibers; e.g. 24 hours, although some dyestuifs react completely in less time.

The term cellulosic yarn as used herein is intended to include natural cellulose yarns such as cotton, and converted cellulose yarns, such as viscose, cuprammonium, nitro-cellulose, triacetate and acetate rayon, and blends thereof.

The term fiber reactive dye as used herein is defined as the group of dyes in which a dyestufi has been coupled with a chemically reactive group, and that react chemically with textile fibers. Examples of the types of fiber reactive dyes are those having the following new Color Index numbers: Reactive Yellow 1, Reactive Yellow 2, Reactive Yellow 3, Reactive Yellow 4, Reactive Yellow 5, Reactive Orange 1, Reactive Orange 2, Reactive Orange 3, Reactive Red 1, Reactive Red 2, Reactive Red 3, Reactive Red 4, Reactive Red 5, Reactive Red 6, Reactive Red 7, Reactive Red 8, Reactive Red 9, Reactive Red 10, Reactive Red 11, Reactive Red 12, Reactive Violet 1, Reactive Violet 2, Reactive Blue 1, Reactive Blue 2, Reactive Blue 3, Reactive Blue 4, Reactive Blue 5, Reactive Blue 6, Reactive Blue 7, Reactive Blue 8, Reactive Brown 1, and Reactive Black 1.

After the dyestulf has reacted with the yarn, the yarn package may be treated in one of several methods, examples of which follow:

a. The dyed package may be tufted into a fabric, while still in its damp condition, and without further treatment. The tufted fabric should be scoured to remove any unreacted dyestutl, and it may be bleached with hydrogen peroxide;

b. If the yarn package is to be stored in its damp condition, a mildew resist agent should be included in the dye composition;

c. After the chemical reaction has taken place, the yarn may be unwound; scoured, with or without peroxide bleaching; dried; and rewound; and

d. After the reaction has taken place, the yarn may be dried in any suitable manner.

In one method of drying the yarn, the yarn Package may be placed on 2. Foster winder; simultaneously unwound and passed in single strand form through a dryer attached to the winder, said dryer being heated to 600 F. and consisting of electrically heated coils wound about a heat-resistant glass (Pyrex) tube 10 long and A2 in diameter; and rewound.

Useful and illustrative examples of the fiber reactive dyestuff composition follow. The components may be compounded in any desired order, although I prefer to have all the water at about 70 F., and to blend just enough water into the dye powder to form a smooth paste. To about 90% of the remaining water are added the wetting agent and mildew resist agent, if such are used, and the dye paste is then added to the 90% fraction. To the remaining approximately 10% of water is added the alkali, which is mixed with the aqueously carried dye just prior to use.

It is recommended that the dyestut'f composition be made fresh before each use to avoid decomposition.

The following components may be added to each gallon of water in the above described manner:

Example 41 Fiber reactive dye (the dyestufii obtained from the reaction of equimolar amounts of cyanuric chloride and the compound obtained by coupling diazotized 2-naphthylarrnne-6:8-disulphonic acid with 4 Example b Fiber reactive dye (the dyestuif obtained from reacting equimolar amounts of cyanuric chloride and the compound obtained by coupling diazotized 4- chloro-S-methyl-Z-aminobenzene sulphonic acid under alkaline conditions with 2-amino-5-naphthol- 7-sulphonic acid (coupled in o-position to the hydroxy group) gms Non-ionic wetting agent (ethylene oxide condensate having 9 mols of oxygen) cc Sodium bicarbonate gms Mildew resist agent (diisobutylphenoxyethoxydimethyl ammonium chloride) gr Example Example d Fiber reactive dye (the dyestutf obtained by coupling diazotized aniline under alkaline conditions with 2-amino-5-naphthol-7-sulphonic acid and diazotizing the monoazo compound obtained and coupling with 2-(4z6' dichloro-s-triazin-2'-yl amino)-5- naphthol-7-sulphonic acid) gms Non-ionic wetting agent (ethylene oxide condensate having 9 mols of oxygen) -cc Sesquicarbonate of soda gms Mildew resist agent (diisobutylphenoxyethoxydimethyl ammonium chloride) gr Example e Fiber reactive dye (the dyestuff resulting when one mol of diazotized p-aminoacetanilide is coupled with one mol of 1-(2':5 '-dichloro-4'-sulfopheny1)- S-methyl-S-pyrazolone, said coupled product hydrolysed and then condensed with equimolar proportions of cyanuric bromide) gms Non-ionic wetting agent (ethylene oxide condensate having 9 mols of oxygen) cc- Sesquicarbonate of soda gms Mildew resist agent (diisobutylphenoxyethoxydimethyl ammonium chloride) gr Example 1 Fiber reactive dye (the dyestutf obtained by coupling diazotized aniline under alkaline conditions with 2-amino-5-naphthol-7-sulphonic acid and diazotizing the monoazo compound obtained and coupling with 2- (4 6'-dichloro-s-triaZin-2-yl amino -5- naphthol-7-sulphonic acid) gms Sesqnicarbonate of soda gms Mildew resist agent (diisobutylphenoxyethoxydimethyl ammonium chloride) gr Example g Fiber reactive dye (the dyestuff resulting when one mol of diazotized p-aminoacetanilide is coupled with one mol of 1-(2':5'-dichloro-4-su1phophenyl)-3-methyl-5-pyrazolone, said coupled product hydrolysed and then condensed with equimolar proportions of cyanuric bromide) gms SesquicarbOnate of soda gms Mildew resist agent (diisobutylphenoxyethoxydimethyl ammonium chloride) gr 6 Example h Example m Fiber reactive dye gms 100 Fiber reactive dye (the dyestufr obtained when one mol of l-amino-4-methylbenzene-3 sulfonic acidbeta-hydroxyethylamide is diazotized and coupled with 1-phenyl-3-methyl-pyrazolone-5 and the free hydroxyl group is esterificd with sulfuric I I acid) gms 2.5

SO2 .OH. CI{2 O SO3H Non-ionic wetting agent (ethylene oxide condensate having 9 mols of oxygen) gms 10 10 Alkali (bicarbonate of soda) gms 10 Mildew resist agent (diisobutylphenoxyethoxydimethy1 ammonium chloride) gr 2.5

Example n Fiber reactive dye (the dyestuir" formed when one mol of diazotized meta-amino-benzenesulfonN- Non-ionic wetting agent (ethylene oxide condensate ethyleneimine is coupled with one mol of l-acetylhaving 9 mols of oxygen) gms 300 amino 8 hydroxy-naphthalene-3:6-disulphonic Sodium hydroxide gms 35 acid) gIIIS 2.5 Mildew resist agent (diisobutylphenoxyethoxydimeth- Non-ionic wetting agent (ethylene oxide condensate yl ammonium chloride) gr 40 having 9 mols of oxygen) gms l0 Alkali (bicarbonate of soda) grns 10 Example I Mildew resist agent (diisobutylphenoxyethoxydimeth- Fiber reactive dye grns 100 yl ammonium chloride) gr 2.5

oorn

| one-011F011 H03S-O-CHz-CHz0zSN=N--N C4119 CH3 Non-ionic wetting agent (ethylene oxide condensate Example 0 having 9 mols of oxygen) cc 300 Fiber reactive dye (the dyestuff obtained when one Sodium bicarbonate -gn1s 100 mol of diazotized 2-amino-8-naphthol-5-sulfonic Mildew resist agent (diisobutylphenoxyethoxydimethacid is coupled with one mol of 1-phenyl-3-sulronyl ammonium chloride) gr 40 beta-Chlorethylamide-chloride) gms 2.5

Example N0n-ionic wetting agent (ethylene oxide condensate Fiber reactive dye (the dye formed when one mol i mols of oxygen) 10 it ah (bicanbonate of soda) gms 10 of 2-(4 -arninophenyl)-6-methyl-benzoth1azoled1- MT 1 new resist agent (.dnsobutylphenoxyethoxydimethsulphonic acid is diazotized and reacted with one 40 l ammonium Chloride) r 2 5 mol of a product formed by reaction of equimolar y amounts of 2-amino-5-hydroxynaphthalene-7-sul- E l phonic acid and the resulting product is reacted Fb with one mol of 1 aminobanzene3 sulphonic 1 er reactive dye (the dyestufi obtained when one acid "gins" 40 mol of dlazotized l-am1no-3:4-d1-chlorobenzene- Non-ionic wetting agent (ethylene oxide condensate sisglfomc acld is coupled f one P of unethhaving 9 mols f oxygen) 200 Y {omega -p p y y y Sodium carbonate gms 40 f Mildew resist agent (diisobutylphenoxyethoxydimeth- E 9 Wetting agent (ethylene oxlde condensate yl ammonium chloride) gr 40 5O zr i ggi i :j g e so a gms Example I: Mildew resist agent (diisobutylphenoxyethoxydimeth- Fiber reactive dye (the dye formed when one mol of yl ammonium chloride) gr 2.5

4-nitro-2-aminophenol is diazotized, the resulting diazotized product coupled with one mol of 2-(4'- Example q Zrninophenyl) amino-S-hydmxymapthalene-l:3'- Fiber reactive dye (the dyestufl? obtained when one i g q afildt the liesultmg lfoduct neutrahzed mol of l-amino-4-br0mo-anthraquinone-2-sulfonic g i l and I efneutr a 1Zed gl acid is condensed with one mol of 1:4 diaminobenfi Wlt one 1110 0 t zene-Z-sulfonic acid and the resulting product is a l 6 acylated with beta-chloropropionic acid chlo- Non-lonlc wetting agent (ethylene oxide condensate 0 Tide) 2 5 h.avmg 9 9 of oxygen) 300 Non-ionic wetting agent (ethylene oxide condensate sgfhum me taslhcate 'j 40 having 9 mols of oxygen) gms 1O Mllilew t gd tylph xy th xy m tn- A Alkali (bicarbonate f soda) 10 y ammomum c onde) Mildew resist agent (diisobutylphenoxyethoxydimeth- Example I yl ammonium chloride) gr 2.5 Fiber reactive dye (the dyestuif obtained when one The above listed examples of fiber reactive dye commolof meta-amino benzene sulfon fluoride is dipositions are all suitable for injection into wound packazotized and coupled With one mol of 1-(4-sulphoages of cellulosic yarn, such as cones, tubes and beams. phenyl)-3 c arboxy-5-pyrazolone) gms 2.5 It will be understood that the volume of dyestuff com- Noln-ionicgwetting fagent (ethylene oxide condensate 10 positionthinjected at each location may be varied, dependav mg mo s 0 oxygen gms ing on e ratio of dyed yarn to undyed yarn that is de- Alkali (bicarbonate of soda) gms 10 sired. It has been found that 10 cc. to 100 cc. of the MllilW resist agenthgdirilolgutylphenoxyethoxydimethabove dyestuff composition per pound or" yarn is dey ammonium c on e gr 2.5 sirable.

'2 Several specific examples of the method of the present invention follow.

Example I Five pounds of undyed cotton yarn, 3,400 yards of 4/2, is Foster wound on a cone 10. The resulting package 11 is of medium density and 7 /2" high, 8" diameter at the top and 9 /2 diameter at the base.

Fifty cc. of the dyestuli of Example a above is drawn into a syringe equipped with an injection needle 0.0080" in diameter, and having openings spaced along its length. The needle is inserted through the wound package of yarn until the needle point touches the cone. The dyestuff is then expelled from the syringe and into a portion 12 of the yarn.

Two hundred and fifty cc. of the dyestuft of Example b above is likewise injected into a second portion 13 of the yarn package.

Five hundred cc. of the dyestufr' of Example above is likewise injected into a third portion 14 of the yarn package.

The package of Wound yarn is allowed to stand at room temperature for 24 hours, following which it may be stored or dried or tufted into a fabric.

Example II Three pounds of undyed viscose rayon yarn, 3,150 yards of 1.25/1, is Foster wound onto a tube to form a package 8 high and 6" diameter, medium density.

Three hundred cc. of the dyestuff composition of Example 1 above is injected into the yarn package in the above described manner.

One hundred and fifty cc. of the dyestuif composition of Example g above is injected into a second location on the yarn package in the manner described above.

Thirty cc. of the dyestutf composition of Example it above is injected into a third location on the yarn package in the above described manner.

The yarn package is allowed to stand at room temperature for 24 hours; wound into skeins; scoured in a bath containing 0.015 oz. of non-ionic detergent (ethylene oxide condensate) and 0.025 oz. of 35% hydrogen peroxide per gallon of water; dried in an oven at 200 F.; and rewound onto tubes. If desired, an equivalent amount of sodium peroxide may be substituted for the hydrogen peroxide in the bleaching composition.

Example III Eight pounds of undyed cupramrnonium rayon yarn,

6,720 yards of 2/2, is Foster wound onto a cone to form This example is identical to Example Ill above, except that 80 cc. each of the dyestuft compositions of Examples 11, i, j, la and l are substituted for the dyestuffs utilized in Example HI.

Example V This example is identical to Example 111 above, except that 90 cc. each of the dyesturT compositions of Examples 111, n, 0, p and q above are substituted for the dyestuif compositions utilized in Example Ill.

Example VI Three pounds of undyed cotton yarn, 50,400 yards of 20/1, is Foster wound onto a cone to form a package of medium density, 6" tall, diameter at the top, and 8" diameter at the base.

Forty-five cc. of the dyestutf composition of Example (1 above is injected into the yarn in the above described manner.

One hundred cc. of the dyestufi composition of Example 0 above is injected into the yarn at a second location on the package, in the above described manner.

Fifty cc. of the dyestufr' composition of Example it above is injected into the yarn at a third location on the package, in the above described manner.

Seventy cc. of the dyestutr" composition of Example i above is injected into the yarn at a fourth location on the cone, in the above described manner.

The wound package of yarn is allowed to stand at room temperature for 24 hours.

The cone of yarn is placed on a Foster winder; unwound; and dried by passing it in single strand form at 100 yards per minute through a heating unit at 600 F. which comprises a heat-resistant glass (Pyrex) tube, 10" long and /2" in diameter, the outside of which is Wound with electric coils; and rewound onto another cone.

Example VII Seven pounds of undyed cotton yarn, 44,100 yards of 30/2, is Foster wound onto a cone, resulting in a package of yarn 8" tall, 7" diameter at the top, 9 /2" diameter at the base, medium density.

Seventy cc. each of the dyestuff compositions of Examples j, k, l, and m above are separately injected into the yarn package at ditferent areas on the package, in the above described manner.

The yarn package is allowed to stand at room temperature for 24 hours.

Example VIII Eight pounds of undyed cotton yarn, 6,720 yards of 2/2, is Foster wound onto a cone, resulting in a yarn package 8" tall, 7 /2" diameter at the top, 10 diameter at the base, medium density.

Eighty cc. each of the dyestulf compositions of Examples n, 0, p, and q above are separately injected into the yarn package at diiferent areas on the package, in the above described manner.

The package of wound yarn is allowed to stand at room temperature for 24 hours.

Example 1X Eight pounds of undyed viscose rayon yarn, 16,800 yards of 5/2, is Foster wound upon a cone, resulting in a yarn package of medium density, 8" tall, 7" diameter at the top and 9" diameter at the base.

One hundred cc. each of the dyestuff compositions of Examples a, b, c, d and e above are separately injected into the yarn package at different places, in the above described manner.

The wound package of yarn is allowed to stand for 24 hours.

Example X This example is identical to Example IX above, except that cc. each of the dyestuff compositions of Examples i, j, k, l and m are substituted for the dyestutr' compositions utilized in Example IX.

Example XI This example is identical to Example IX above, except that cc. each of the dyestutf compositions of Examples n, 0, p and q are substituted for the dyestuif compositions utilized in Example IX.

There are numerous methods of producing fabrics having a random dyed effect from the above yarn. For example, the random dyed yarn may be utilized in the conventional manner for forming the entire pile of a tufted rug or carpet, and the resulting rug or carpet may be overdyed if desired. Woven fabrics may be produced from the above yarn, using it in the warp or filling, or both, and it may be interwoven with dycd or undyed warp and filling yarns in any desired manner;

the resulting woven fabric may be overdyed if desired. Other methods of utilizing the yarn of the present invention Will become readily apparent to those skilled in the art of fabric construction.

I claim:

1. In the method for random dyeing cellulosic yarn wherein liquid dye composition is injected into at least one selected portion of a Wound package of yarn to provide a yarn having dyed areas and undyed areas of varying lengths occurring at random along the yarn, the improvement comprising the steps of utilizing a dye cornposition comprising fiber reactive dye, Water and alkali as the liquid dye composition injected into the wound package of yarn, and permitting the injected wound package of yarn to stand until the fiber reactive dye has reacted chemically With the yarn.

2. In the method according to claim 1 and further 10 characterized in that the dye composition utilized also contains wetting agent, and also further characterized in that the yarn is scoured and dried after said fiber reactive dye has reacted chemically with the yarn.

3. In the method according to claim 1 and further characterized in that the dye composition utilized is injected at 70 F.

References Cited in the file of this patent UNITED STATES PATENTS 1,584,335 Van Ness May 11, 1926 2,150,309 Atwell Mar. 14, 1939 2,978,289 Barker et al Apr. 4, 1961 3,040,022 Starn June 19, 1962 3,043,650 Wegmann et a1 July 10, 1962 

1. IN THE METHOD FOR RANDOM DYEING CELLULOSIC YARN WHEREIN LIQUID DYE COMPOSITION IS INJECTED INTO AT LEAST ONE SELECTED PORTION OF A WOUND PACKAGE OF YARN TO PROVIDE A YARN HAVING DYED AREAS AND UNDYED AREAS OF VARYING LENGTHS OCCURRING AT RANDOM ALONG THE YARN, THE IMPROVEMENT COMPRISING THE STEPS OF UTILIZING A DYE COMPOSITION COMPRISING FIBER REACTIVE DYE, WATER AND ALKALI AS THE LIQUID DYE COMPOSITION INJECTED INTO THE WOUND PACKAGE OF YARN, AND PERMITTING THE INJECTED WOUND PACKAGE OF YARN TO STAND UNTIL THE FIBER REACTIVE DYE HAS REACTED CHEMICALLY WITH THE YARN. 